WO2006043470A1 - Negative electrode for battery and battery using same - Google Patents

Negative electrode for battery and battery using same Download PDF

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Publication number
WO2006043470A1
WO2006043470A1 PCT/JP2005/018917 JP2005018917W WO2006043470A1 WO 2006043470 A1 WO2006043470 A1 WO 2006043470A1 JP 2005018917 W JP2005018917 W JP 2005018917W WO 2006043470 A1 WO2006043470 A1 WO 2006043470A1
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Prior art keywords
active material
material layer
negative electrode
tin
lithium
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PCT/JP2005/018917
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French (fr)
Japanese (ja)
Inventor
Masaya Ugaji
Shinji Mino
Yasuyuki Shibano
Shuji Ito
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Matsushita Electric Industrial Co., Ltd.
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Priority to JP2004-306649 priority Critical
Priority to JP2004306649 priority
Application filed by Matsushita Electric Industrial Co., Ltd. filed Critical Matsushita Electric Industrial Co., Ltd.
Publication of WO2006043470A1 publication Critical patent/WO2006043470A1/en

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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/04Processes of manufacture in general
    • H01M4/049Manufacturing of an active layer by chemical means
    • H01M4/0495Chemical alloying
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134Electrodes based on metals, Si or alloys
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1395Processes of manufacture of electrodes based on metals, Si or alloys
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381Alkaline or alkaline earth metals elements
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40Alloys based on alkali metals
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M2004/026Electrodes composed of or comprising active material characterised by the polarity
    • H01M2004/027Negative electrodes

Abstract

Disclosed is a negative electrode for batteries which comprises a collector, an active material layer and an inorganic compound layer. The active material layer is formed on the collector, and the inorganic compound layer is formed on the surface of the active material layer. The general formula of the inorganic compound layer is expressed as LixPTyOz or LixMOyNz. The compound constituting the inorganic compound layer has lithium ion conductivity and excellent moisture resistance.

Description

 Specification

 Battery negative electrode and battery using the same

 Technical field

 The present invention relates to a negative electrode having a negative electrode active material layer and an inorganic compound layer, and a battery using the same.

 Background art

 [0002] In recent years, with the development of portable devices such as personal computers and mobile phones, the demand for batteries as power sources has increased. Batteries used in such applications are required to be used at room temperature, and at the same time, a high energy density and excellent cycle characteristics are required.

 [0003] In response to such a demand, an organic electrolyte, or a gel polymer electrolyte that has been made non-fluidized using a polymer or a gelling agent, and various nonaqueous electrolytes such as a solid electrolyte are used as the electrolyte. Non-aqueous electrolyte lithium batteries using lithium ions as a charge transfer medium have been developed. In addition, lithium cobaltate (LiCoO), lithium nickelate (LiNi

 2

 O), lithium manganate (LiMn O), etc.

2 2 4

 Have been found to be reversibly occluded and released and exhibit a high reversible potential, and these materials have been utilized as positive electrode active materials. On the other hand, simple substances, alloys or compounds having a low reversible potential such as graphite and various carbon bodies have been discovered, and these have been utilized as negative electrode active materials. In addition, lithium batteries using these materials that absorb and release lithium ions as active materials have been developed.

[0004] Lithium batteries have a much larger voltage and energy density than aqueous batteries, and currently occupy the mainstream of small batteries. In particular, batteries using carbon-based materials for the negative electrode have been recognized for manufacturing safety and reliability in terms of practical use. However, the current increase in capacity of carbon-based materials has reached its maximum theoretical capacity and is at its limit. Since the energy density of the battery is largely governed by the capacity density of the negative electrode material, a new lithium ion storage / release material is being sought to further improve the energy density. [0005] Among them, a simple substance of either silicon (Si) or tin (Sn), or an alloy material containing one or more of these elements is promising as a material excellent in reversible capacity that can replace carbon-based materials. Is being viewed. However, when these materials are used in direct contact with an organic electrolyte, the characteristics are likely to deteriorate. In addition, these materials may occlude and release a large amount of lithium ions, so that the crystal becomes finer and the shape collapses, or the bonding with the current collector becomes incomplete and the life characteristics are impaired.

 [0006] Therefore, it has been proposed to form an inorganic compound layer having ion conductivity at the interface between the negative electrode active metal material and the electrolyte so that the negative electrode and the electrolyte are isolated. In this case, the occlusion / release reaction of lithium ions to the negative electrode is performed through the inorganic compound layer. As such lithium ion conductive inorganic compounds, for example, Japanese Patent Application Laid-Open No. 2004-171875 discloses lithium halides such as lithium fluoride and lithium iodide, lithium phosphate (Li PO

 3 4

More preferably, lithium phosphate nitride (LIPON) is disclosed as a material.

[0007] In general, minute moisture at the lOppm level that cannot be easily removed remains in the electrolyte. Here, the above-mentioned Li PO and LIPON are in very small amounts when exposed to moisture.

 3 4

 However, phosphorus (P), which originally existed in the pentavalent state, is reduced to phosphorus with a low acid number. As a result, Li PO and LIPON are decomposed and the ionic conductivity is remarkably lowered. As a result, the negative electrode active

3 4

 The inorganic compound layer formed on the surface of the conductive metal material becomes a resistance, the impedance of the whole negative electrode increases, and the battery characteristics deteriorate.

 Disclosure of the invention

 [0008] The negative electrode for a battery of the present invention includes an active material layer and a lithium ion conductive inorganic compound layer (hereinafter sometimes referred to as an inorganic compound layer) provided on the active material layer. The active material layer includes at least one of a simple substance of Sn or Si, an alloy containing at least one of these elements, or a group of compound forces. The inorganic compound layer is composed of a compound having a chemical composition represented by any of the following general formula 1 or general formula 2.

 [0009] General formula 1: Li PTO; where component T is an element consisting of element symbols Ti, Cu, Zr, Mo, Ta, W x yz

At least one element selected from the prime group force, which is powerful 2. 0≤x≤7.0, 0.01≤y≤l.0, 3.5≤z≤8.0, preferably 2 0≤x≤3.0, 0.01≤y≤0.50, 3.5≤z≤4.0. [0010] General formula 2: Li MO N, where M is the element symbol Si, B, Ge, Al, C, Ga and S

 At least one element selected from the element group force, with the strength 0. 6≤x≤l. 0, 1. 05≤y ≤ 1.99, 0. 01≤z≤0. 5, or 1. 6≤x≤2. 0, 2. 05≤y≤2. 99, 0. 01≤z≤ 0.5, or ί 1. 6≤χ≤2.0, 3. 05≤y≤3. 99 0. 01 ≤ ζ ≤ 0.5, and ί 4. 4.6 ≤ χ ≤ 5.0, 3. 05 ≤ y ≤ 3.99, 0. 01 ≤ ζ ≤ 0.5.

[0011] Since the compounds constituting these inorganic compound layers have high lithium ion conductivity and excellent moisture resistance, a decrease in lithium ion conductivity is suppressed even in contact with an electrolyte in which moisture remains. As a result, excellent battery characteristics are maintained over a long charge / discharge cycle. That is, the stability of the negative electrode itself having an active material layer that occludes and releases lithium ions to water and the cycle characteristics of a battery using such a negative electrode are greatly improved.

 Brief Description of Drawings

 [0012] FIG. 1 is a schematic cross-sectional view showing the basic structure of the battery and the negative electrode used therefor in Embodiments 1 and 2 of the present invention.

 FIG. 2 is a cycle characteristic diagram according to the first embodiment of the present invention.

 FIG. 3 is a diagram showing the relationship between WZP and capacity retention rate in the composition of the inorganic compound layer in Embodiment 1 of the present invention.

 FIG. 4 is a diagram showing the relationship between WZP and capacity retention rate in the composition of the inorganic compound layer in Embodiment 1 of the present invention.

 FIG. 5 is a diagram showing the relationship between NZSi and the capacity retention rate in the composition of the inorganic compound layer in the second embodiment of the present invention.

 Explanation of symbols

[0013] 1 negative electrode

 2 Positive electrode

 3 Electrolyte

 4 Gasket

 5 Lid

6 cases 7 Positive current collector

 8 Positive electrode active material layer

 9 Current collector

 10 Negative electrode active material layer

 11 Inorganic compound layer

 BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention is not limited to the following contents as long as it is based on the basic features described in this specification.

[0015] (Embodiment 1)

 FIG. 1 is a cross-sectional view of a battery using a negative electrode according to Embodiment 1 of the present invention. The battery includes a negative electrode 1, a positive electrode 2 that faces the negative electrode 1 and reduces lithium ions during discharge, and an electrolyte 3 that is interposed between the negative electrode 1 and the positive electrode 2 and conducts lithium ions. The negative electrode 1 and the positive electrode 2 are accommodated in the case 6 using the gasket 4 and the lid 5 together with the electrolyte 3. The positive electrode 2 includes a positive electrode current collector 7 and a positive electrode active material layer (hereinafter referred to as an active material layer) 8 containing a positive electrode active material. The negative electrode 1 includes a current collector 9, a negative electrode active material layer (hereinafter referred to as an active material layer) 10 provided on the surface thereof, and a lithium ion conductive inorganic compound layer 11 formed on the surface of the active material layer 10. Have

 [0016] In the active material layer 10, in addition to tin (Sn) and silicon (Si) as active material materials that occlude and release lithium ions, Ni Sn, Mg Sn ゝ SnO (0 <x <2), SnO, SiB, SiB, Mg Si ゝ Ni

 3 4 2 x 2 4 6 2

Si, Ni Si, TiSi, TiSi, MoSi, CoSi, CaSi, CrSi, Cu Si, FeSi, MnSi, N

2 2 2 2 2 2 5 2 2 bSi, TaSi, VSi, WSi, ZnSi, SiC, Si N, Si N 0, SiO (0 <x <2), SiN (

2 2 2 2 2 3 4 2 2 x y where 0 <y <4Z3), SiO, SnSiO, LiSnO, etc.

 twenty three

An alloy, a compound, or a solid solution can be applied. These may constitute the active material layer 10 alone, or a plurality of them may constitute the active material layer 10 at the same time. Examples in which a plurality of types simultaneously constitute the active material layer 10 include a compound containing Si, oxygen, and nitrogen, and a composite of a plurality of compounds containing Si and oxygen and having different ratios of Si and oxygen. . Thus, the active material layer 10 is composed of a simple substance of Sn, a simple substance of Si, an alloy containing at least one of Sn and Si, It includes at least one of the group consisting of compound powers including at least one of Sn and Si.

[0017] The current collector 9 is made of a metal or alloy that is less reactive than lithium, and a conductor plate or sintered body having an arbitrary shape is formed and used. For example, in addition to copper (Cu) and nickel (Ni), one or more simple substances selected from titanium (Ti), molybdenum (Mo), tantalum (Ta), iron (Fe) and carbon (C) force, or these It is possible to use alloys, steel, stainless steel, etc. containing at least one kind. In particular, it is preferable to select conductive materials that can easily form alloys with metals that are active materials, such as Cu and Ni. Thus, when the active material layer 10 contains a metal, it is preferable that the metal of the active material layer 10 is alloyed with the current collector 9 at a part of the interface with the current collector 9. As a result, the active material layer 10 and the current collector 9 are more firmly bonded, so that excellent battery characteristics are maintained over a long charge / discharge cycle.

Such an alloy is preferably formed when the active material layer 10 is formed on the current collector 9 using an active material. As a method for forming such an alloy, a method in which a molded active material layer is bonded to a current collector surface, a method in which an active material component powder is applied, a method in which a plating layer is formed, vapor deposition, sputtering, or the like is used. A layer forming method is applicable. The form of the alloy may be either an intermetallic compound or a solid solution. In addition, if necessary, a thin film of the above current collector material may be formed by using a self-shape-holding support such as an oxide such as silica or carbon, and using sputtering or the like thereon. For alloying at the interface, it is preferable that heat treatment for promoting alloying, such as sintering, be provided after the formation of the active material layer 10. By such alloying, the active material layer 10 and the current collector 9 are more firmly bonded, and thus excellent battery characteristics are maintained over a long charge / discharge cycle.

The inorganic compound layer 11 is made of a compound having a chemical composition represented by Li PTO. Component T is an element symbol Titanium (Ti), Copper (Cu), Zirconium (Zr), Molybdenum (Mo), Tantalum (Ta), Tungsten (W) Force Group force 2. 0≤x≤7.0, 0.01≤y≤l.0, 3.5≤z≤8.0. Desirably 2. 0≤x≤3.0, 0.01≤y≤0.50, 3.5≤z≤4.0, or 2. 0≤x≤3.0, 0.01≤y≤l 0, 3.5 ≤z≤7.0. The above Li PTO is a material with excellent lithium ion conductivity and moisture resistance discovered by the present inventors, and is disclosed in JP-A-2004-335455. [0020] In addition to the above as component T, vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), niobium (Nb), ruthenium (Ru ), Silver (Ag), platinum (Pt), and gold (Au) forces. Element group force may be at least one selected element. These elements are similar in nature to Ti, Cu, Zr, Mo, Ta, and W, and it can be reasonably inferred that the same effect can be obtained even when any of these powers is added.

 [0021] Li PTO is composed of a constituent element component of lithium phosphate and a transition metal group T.

 When this compound is in contact with water molecules, the transition metal component τ is considered to be reduced in preference to the phosphorus atom. Therefore, decomposition of the lithium phosphate component is suppressed, and a decrease in ion conductivity of the inorganic compound layer 11 itself is suppressed. As described above, in Li PTO, the presence of the transition metal component τ may suppress the reduction of phosphorus. Therefore, the transition metal component τ may be incorporated into the lithium phosphate at the atomic level or may be mixed with the lithium phosphate at the particle level.

 [0022] In addition, when the metal component T is an oxide, the metal component T may be partially incorporated into lithium lithium phosphate at an atomic level, or may be mixed with lithium phosphate at the particle level. What! /

 [0023] When the metal component T is a lithium oxide, the lithium phosphate and the lithium oxide of the metal component T form a solid solution or are mixed at the particle level. It can be mixed at the particle level with the product and lithium oxide.

 [0024] Li PTO has excellent ionic conductivity and suppresses the decomposition of ionic conductive solids in a humid environment. 2. 0≤χ≤7.0, 0.01≤ It is desirable that y≤l. 0, 3.5≤z≤8.0. This composition uses a transition metal as a target for the transition metal component T when forming Li PTO, in the case of 2.o≤x≤3.0, 0.01 ≤y≤0.50, 3. It is desirable that 5≤z≤4.0. When a transition metal oxide is used as the target, the power of 2. 0≤x≤3.0, 0.01≤y≤l. 0, 3.5≤z≤ 7 ^ desirable! / ヽ. When lithium transition metal oxide is used as the target, it is desirable that 2.0 ≤ x ≤ 7.0, 0. 01 ≤ y ≤ l. 0, 3.5 ≤ z ≤ 8.0 .

[0025] Next, each layer forming the negative electrode 1 will be described. As shown in FIG. 1, the current collector 9, the active material layer 10, and the inorganic compound layer 11 are preferably laminated in order. At that time, the formation area and shape of each layer are arbitrary, but the active material layer 10 is completely covered with the inorganic compound layer 11. I like it. In the case of a battery configuration in which both sides of the negative electrode 1 are! / And the deviation faces the positive electrode 2, a configuration in which the active material layer 10 and the inorganic compound layer 11 are provided on both sides of the positive electrode 2 is preferable. The thickness of the inorganic compound layer 11 is arbitrary, but it is preferably a thin film having a thickness of 0.05 to LO m in consideration of the ability to protect against a moist environment, impedance, physical strength, and the like.

[0026] For the formation of the inorganic compound layer 11, a method in which Li PTO is mixed and applied together with a binder such as polyvinylidene fluoride can be applied. Alternatively, lithium phosphate and component T, such as transition metals such as W, Mo, and Ta, or their metal oxides are used as a target or vapor deposition source and formed by a dry thin film process. In other words, various deposition methods such as vapor deposition method, resistance heating vapor deposition method, high frequency heating vapor deposition method, laser ablation vapor deposition method, ion beam vapor deposition method, sputtering method, rf magnetron sputtering method, etc. in argon or vacuum environment It is preferable to form on the active material layer 10 by applying a thin film forming method. Also, instead of lithium phosphate, a mixture of Li 2 O and PO 2 may be applied as a target or a deposition source.

 2 2 5

 Yes.

 In such an inorganic compound, the valences of the lithium atom, the phosphorus atom, and the oxygen atom are +1 valence, +5 valence, and 2 valence, respectively. The transition metal element component T has the same valence in the state of the compound when the compound is used as the target. On the other hand, when a transition metal unit is used as a target, component T is considered to be incorporated in the lithium phosphate in a metallic state.

 [0028] In the method of obtaining x, y, and z in the prepared Li PTO, the ratio of phosphorus atoms is first set to 1. Next, y is calculated by calculating the ratio between component T and phosphorus atom, including the force of inductively coupled plasma spectroscopy (ICP spectroscopy). Furthermore, z is calculated by calculating the ratio of oxygen to phosphorus atoms or transition metal atoms by techniques such as nitrogen oxygen analysis. In the nitrogen-oxygen analysis, for example, oxygen and nitrogen contained in the material are extracted by an inert gas inson heating / melting method, which is thermal decomposition at a high temperature. Then, oxygen is detected as CO gas by a highly sensitive non-dispersive infrared detector, and nitrogen is detected as N gas and highly sensitive heat transfer.

 2

 It can be detected by a conductivity detector. X is calculated using the above valence, assuming that the overall valence is zero.

[0029] Electrolyte 3, case 6 and other components generally include lithium compounds and lithium All materials and shapes used in batteries constructed by applying an alloy to the negative electrode are applicable. The material of the active material layer 8 includes LiCoO, LiNiO, LiMn O, or a mixture thereof.

 2 2 2 4

 Alternatively, a material that reversibly stores and releases lithium ions electrochemically, such as a composite compound, is used.

 [0030] For the electrolyte 3, an electrolyte solution in which a solute is dissolved in an organic solvent, or a so-called polymer electrolyte layer containing these and made non-fluidized with a polymer can be applied. At least when an electrolyte solution is used, it is preferable to use a separator such as polyethylene between the positive electrode 2 and the negative electrode 1 and impregnate the solution. Electrolyte 3 may be solid.

 [0031] The material of the electrolyte 3 is selected based on the oxidation-reduction potential of the active material contained in the positive electrode 2. When the electrolyte 3 is an organic electrolyte, preferred solutes to be used are lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitride, lithium phosphate, lithium silicate, lithium sulfide, phosphide Salts generally used in lithium batteries, such as lithium, can be applied. In addition, organic solvents for dissolving such supporting salts include propylene carbonate, ethylene carbonate, gethinole carbonate, methinoreethino carbonate, dimethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, and γ-butyl. Lataton, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methylol 1,3-dioxolane, jetyl ether, sulfolane, acetonitrile, propylnitrile, azole, acetate, propionate, etc. Alternatively, a solvent used in a lithium battery such as a mixture of more than that can be applied. When the electrolyte 3 is a solid, the electrolyte 3 is preferably composed of Li PTO constituting the inorganic compound layer 11. In this case, moisture enters the inorganic compound layer 11 directly from the battery external force.

[0032] Even when the negative electrode 1 has the above-described configuration, the inorganic compound layer 11 protects the active material layer 10 and a battery having good characteristics can be obtained. That is, by preparing the negative electrode 1 as described above, the moisture resistance of the negative electrode 1 is increased, and deterioration of charge / discharge cycle characteristics of a battery using the negative electrode 1 is suppressed. Such a negative electrode 1 can be applied to all lithium batteries that use a negative electrode active material that can store and release lithium, or S or Sn as a simple substance, a compound, or an alloy. Improved characteristics.

[0033] When the battery is charged and discharged, lithium ions are directly applied to the electrolyte 3 through the inorganic compound layer 11. It is occluded by the active material layer 10 that is not in contact with it and functions as a negative electrode for the first time. That is, the inorganic compound layer 11 faces the electrolyte 3 and serves as a migration path of lithium ions to the active material layer 10 isolated from the electrolyte 3. In this configuration, even if the electrolyte 3 contains moisture, the inorganic compound layer 11 can continue the role of the ion transfer path without being affected by the moisture of the electrolyte 3.

[0034] The features and effects of Embodiment 1 according to the present invention will be described below with specific examples. As an example, an active material layer 10 was formed on a current collector 9 made of Cu as described below, and an inorganic compound layer 11 made of a compound having a chemical composition represented by Li PTO was formed thereon.

 [0035] In Samples 1 to 6, first, Si was used as a negative electrode active material material by using an electron beam vacuum deposition method on a current collector 9 having a thickness of 35 μm and a surface roughness of 2 μm and having an electrolytic copper foil force. An active material layer 10 having a thickness of 3 m was formed. Si with a purity of 99.9999% was used as the target. After reducing the pressure in the vacuum chamber, the acceleration voltage was set to -8 kV, the emission was set to 500 mA, and the target was irradiated with an electron beam. The Si vapor was deposited on the current collector 9 installed on the fixed base, and an active material layer 10 such as S was formed. The deposition time was 20 minutes. The obtained negative electrode 1 was cut, and the vicinity of the interface between the current collector 9 and the active material layer 10 was subjected to XPS (X-ray Photoele ctron Spectrscopy) and AES (Auger Electron Spectr scopy). When analyzed by spectroscopy, at least a part of the interface was alloyed.

 In Sample 7, an active material layer 10 having a thickness of 3 m using Sn as a negative electrode active material was formed on a current collector 9 similar to Sample 1 using an electrolytic plating method. For the electrolytic plating, a plating bath having the composition shown in (Table 1) was used, and metallic tin was used for the anode of the counter electrode. Then, the negative electrode 1 on which the active material layer 10 was formed was vacuum-treated and heat-treated at 200 ° C. for 10 hours.

 [0037] [Table 1]

In sample 8, 50 wt.% By rf sputtering method on current collector 9 similar to sample 1. An active material layer 10 having a thickness of 1.5 / zm using% Si-50 wt% TiSi as an active material was produced. that time

 2

 Then, a chip-like Ti metal was placed on a Si target having a diameter of 4 inches, and sputtered with an rf power of 500 W for 1 hour in an argon atmosphere of 2 Pa. As in sample 1, when the vicinity of the interface between current collector 9 and active material layer 10 is analyzed by XPS and AES, active material layer 10 and current collector 9 are bonded by alloying at least part of the interface. It was confirmed that

[0039] In sample 9, 50 wt% Sn was applied to current collector 9 similar to sample 1 by rf sputtering.

 -Thickness using 50wt% NiSn as active material 1. An active material layer 10 of O / zm was prepared. that time,

 3 4

 Using a mixture of Sn and NiSn with a diameter of 4 inches as a target, in a 3 Pa argon atmosphere

 3 4

 Sputtered at 100W rf power for 20 minutes.

 [0040] Similarly to Samples 1 to 6, Samples 7 to 9 were analyzed by XPS and AES in the vicinity of the interface between current collector 9 and active material layer 10, and active material layer 10 and current collector 9 had less interfaces. It was confirmed that some parts were alloyed and joined.

 [0041] In sample 10, an active material layer 10 having a thickness of 1. O / zm using SiO (0 <x <2) as an active material is deposited on the same current collector 9 as in sample 1 by electron beam vacuum deposition. Made. Si with a purity of 99.9999% was used as the target. After reducing the pressure in the vacuum chamber, oxygen gas having a purity of 99.7% was introduced into the nozzle force chamber at a flow rate of 80 sccm. Furthermore, the acceleration voltage was set to -8kV, the emission was set to 500mA, and the target was irradiated with an electron beam. After passing through the oxygen atmosphere, the Si vapor was deposited on the current collector 9 installed on the fixed base, and an active material layer 10 having SiO force was formed. The deposition time was 20 minutes. When the amount of oxygen contained in the obtained active material layer 10 was quantified by a combustion method, it was confirmed that the composition of this compound was Si 2 O 3.

 0.5

 Next, for each sample, an inorganic compound layer 11 having a thickness of 500 nm and made of Li PTO was formed on the active material layer 10 by rf sputtering. At that time, Li PO with a diameter of 4 inches and a transition metal element as shown in Table 2 were used as targets. And 5mTor

3 4

 100 rf power, transition metal component for Li PO in an argon atmosphere of r

 3 4

For T, 25W rf power was applied and sputtering was performed for 10 minutes. The thickness of the formed inorganic compound layer 11 was about 0.15 m. In addition, the composition of the formed inorganic compound layer 11 is such that platinum is placed beside the current collector 9 on which the active material layer 10 was formed when the inorganic compound layer 11 was formed. The sample was prepared by installing the plate and analyzed by ICP spectroscopy. According to this method, the composition of the composition was Li PTO.

 2. 8 0. 2 3. 9

 [0043] Sample 1 ~: In order to compare the characteristics of LO with the conventional structure, a comparative sample in which a layer that also has a lithium phosphate (LIPON) force instead of the inorganic compound layer 11 of Sample 1 was formed. 1 to 5 were produced. The active material layers 10 of Comparative Samples 1 to 5 were the same as Samples 1, 7, 8, 9, and 10, respectively. In forming the LIPON layer, a mixed gas of argon and nitrogen gas was used as the discharge gas, and Li PO was used as the target. The thickness of the LIPON layer is about 0

 3 4

 2 m. Except this, it was the same as Sampu Nore 1, 7, 8, 9, 10. (Table 2) shows the configurations of Sampu Nore 1 to 10 and Comparative Sampu Nore 1 to 5.

[0044] [Table 2]

 Next, in order to evaluate the cycle characteristics of the various negative electrodes 1 produced in this way and batteries using these, the positive electrode 2 using LiCoO as an active material is used as shown in FIG.

 2

 A coin-type secondary battery was produced.

[0046] The positive electrode 2 was produced as follows. First, the positive electrode active material LiCoO and the conductive agent

 2

Tylene black and poly (vinylidene fluoride) as a binder were mixed at a weight ratio of 90: 5: 5. This mixture was dispersed in N-methylpyrrolidone to prepare a positive electrode paste. Next, this positive electrode paste was applied onto a positive electrode current collector 7 made of an aluminum foil by a doctor blade method, heated and dried, and then pressed to form an active material layer 8. Next, positive current collector 7 A case 6 to be a positive electrode terminal was attached to the.

[0047] The electrolyte 3 was prepared by dissolving 1 mol / L of LiPF in a mixed solvent of ethylene carbonate and ethylmethyl carbonate mixed at a volume ratio of 1: 1. Using this solution as a separator

 6

 It was used by being immersed in a polyethylene microporous membrane having a porosity of about 40% and a thickness of 30 m, which is usually commercially available. When the moisture content of electrolyte 3 is measured by the Karl Fischer method, it reaches 12 ppm.

 [0048] A coin-type battery having a diameter of 20 mm and a height of 1.6 mm was manufactured using the above-described components. At that time, the case 5 enclosing the positive electrode 2 was covered with the lid 5 enclosing the negative electrode 1, and force squeezed and sealed through the gasket 4. The battery was designed so that the charge / discharge capacity of the positive electrode 2 was twice the charge / discharge capacity of the negative electrode 1, and the battery was configured with negative electrode capacity restrictions.

 Next, each battery was housed in a constant temperature bath at a temperature of 20 ° C., and a charge / discharge cycle test was performed. At that time, the battery was charged at a constant current until the battery voltage reached 4.2 V at a current value at which the design capacity was discharged in 5 hours, that is, at a 5-hour rate. Then, it switched to 4.2V constant voltage charge and charged until the current value dropped to 5% of the constant current charge value. During discharging, constant current discharging was performed until the battery voltage reached 2.5 V at the same current value as during constant current charging, and the discharge capacity was measured. In this way, the ratio of the discharge capacity during the cycle to the initial discharge capacity, that is, the change in the capacity maintenance ratio was examined. In addition, the capacity retention after 100 cycles was compared as necessary. When the battery was disassembled after charging and the negative electrode 1 was examined, it was confirmed that lithium was occluded in the active material layer 10.

 FIG. 2 shows the relationship between the capacity retention ratio and the number of cycles (cycle characteristics) between the battery of sample 1 and the battery of comparative sample 1. As is apparent from the figure, the capacity retention rate of the comparative sample 1 in which LIPON was formed as a conventional ionic conductor in the inorganic compound layer was reduced early. In contrast, the sample 1 battery in which tungsten W was selected as the component T and the inorganic compound layer 11 made of a compound having a chemical composition represented by the general formula Li PTO was formed was markedly different from the comparative sample 1. The cycle characteristics were improved.

[0051] (Table 2) shows the results of comparing the capacity retention rates after 100 cycles. In Comparative Samples 1 to 5 using an inorganic compound layer made of LIPON, the capacity retention rate is about 40%. On the other hand, the batteries of Samples 1 to 10 in which the inorganic compound layer 11 of the present invention was formed were 100 Even after the cycle has elapsed, the capacity retention rate of approximately 60% or more is maintained, and excellent cycle characteristics are exhibited.

 [0052] As described above, since the cycle characteristics are improved by forming the inorganic compound layer 11 with a compound having a chemical composition represented by the general formula Li PTO, this improvement is achieved by the active material layer 1

It is considered that it does not depend on the composition of 0. Therefore, the following examination was performed only when the samples 1 to 6 had the active material layer 10.

[0053] Next, the results of studying the range of the y value in the general formula LiPTO are shown. Here, as an example, a case where tungsten (W) is applied as the component T will be described.

[0054] As shown in Table 3, Samples 1A to 1H were prepared. In these preparations, an inorganic compound layer 11 made of a compound having a chemical composition represented by Li PW O in which WZP, which is the molar ratio of W and P, is changed by changing the sputtering rf power in the configuration of Sample 1 is used. Formed. WZP corresponds to y in the composition formula. Other conditions were the same as for sample 1. WZP was 0.005, 0.01, 0.05, 0.1, 0.2, 0.5, 0.6, and 0.8 for samples 1A to LH, respectively.

[0055] [Table 3]

[0056] Using these samples, batteries were fabricated and evaluated in the same manner as Sample 1. In other words, the negative electrode formed by forming Li PW O having different WZP molar ratios (y) in the inorganic compound layer 11 was used for charging and discharging under the same conditions as described above. I went. Figure 3 shows the relationship between the capacity retention rate at the 100th cycle and WZP, which is obtained as a result. As is apparent from Fig. 3, when the WZP is 0.01 or more and 0.5 or less, the capacity retention rate at the 100th cycle is 0% or more, and good characteristics are shown. Next, the case where the raw material of the inorganic compound layer 11 is changed will be described. First, the case where the transition metal oxide shown in (Table 4) is used in place of the transition metal element component T alone when forming the inorganic compound layer 11 will be described.

 [0058] [Table 4]

 Active material layer: S i

[0059] Negative electrode 1 was formed in the same manner as Sample 1, except that the transition metal oxide shown in Table 4 was used as the sputtering target. Using the obtained negative electrodes 1 of samples 1J to 6J, batteries were produced. The composition of the inorganic compound layer 11 in Samples 1J to 6J is shown in (Table 4). The capacity retention rate after 100 cycles, which is the result of evaluating the obtained battery under the same conditions as described above, is shown in (Table 4).

 [0060] (Table 4) As is clear from the force, the comparative sample 1 had a capacity retention rate of 43.4%, whereas the inorganic compound layer also had a compound force having a chemical composition represented by Li PTO. The batteries of samples 1J to 11 that formed 11 showed a capacity retention rate of 60% or more even after 100 cycles, and showed excellent cycle characteristics. Thus, the cycle characteristics were improved even when transition metal oxides were used as raw materials in addition to the transition metal alone. In addition to the transition metal oxides shown in (Table 4), pentanoic acid vanadium (V O), triacidic chromium (Cr O), diacid

 2 5 2 3 Manganese (MnO), iron oxide (Fe 2 O 3), cobalt oxide (Co 2 O 3), nickel oxide (NiO)

 2 3 4 3 4

 , Niobium pentoxide (Nb 2 O 3) and acid silver (Ag 2 O) can be used to achieve the same effect.

 2 5 2

 Can be guessed.

Next, when the inorganic compound layer 11 is formed, a lithium-containing transition metal oxide as shown in (Table 5) is used as a target instead of a single transition metal element component. explain. [0062] [Table 5]

 Active material layer: S i

[0063] Negative electrode 1 was formed in the same manner as Sample 1, except that the lithium-containing transition metal oxide shown in (Table 5) was used as the sputtering target. Using the obtained samples 1K to 4K, negative electrode 1 of 6 mm, a battery was produced. The composition of the inorganic compound layer 11 in Samples 1 to 4 and 6 is shown in (Table 5). (Table 5) shows the capacity retention rate after 100 cycles, which is the result of evaluating the obtained battery under the same conditions. As can be seen from (Table 5), the capacity retention rate of Comparative Sample 1 was 43.4%, while Li PT

A sample 1K to 4K, 6mm battery with an inorganic compound layer 11 having a chemical composition represented by 0 has a capacity retention rate of 60% or more even after 100 cycles, and excellent cycle characteristics showed that. As described above, even when a lithium-containing transition metal oxide is used as a raw material in addition to a single transition metal, the cycle characteristics are improved.

[0064] Next, the results of study on the y value when a lithium-containing transition metal oxide is used instead of the single element of the transition metal element component as a target when forming the inorganic compound layer 11 are shown. As an example, the case where lithium tungstate (Li WO) is used will be explained.

 twenty four

 Light up.

[0065] (Table 6) Samples 1KA ~: LKF were prepared as shown. In these preparations, the composition of sample 1K was changed to an inorganic material consisting of a compound having a chemical composition represented by Li PW O with different WZP, which is the molar ratio of W and P, by changing the sputtering rf power. Compound layer 11 was formed. WZP corresponds to y in the composition formula. The other conditions were in accordance with sample 1K. W / Pi, Sampu Nore 1KA ~: It was 0.01, 0.1, 0.25, 0.33, 1.0, 2.0 for LKF, respectively. (Table 6) shows the composition of each of the Sampnore 1KA ~: LKF inorganic composite layers. [0066] [Table 6]

 Active material layer: S i

 [0067] Using these samples, batteries were fabricated and evaluated in the same manner as Sample 1K. Figure 4 shows the capacity retention rate and the WZP after 100 cycles when a battery using the negative electrode 1 formed by forming Li PWO with different WZP in the inorganic compound layer 11 was used. Shows the relationship. As is clear from FIG. 4, the capacity retention ratio was 0.01 or more and 1.0 or less when the capacity retention ratio was 60% or more, indicating good characteristics.

[0068] Comparing FIG. 3 and FIG. 4, the same results are obtained when Li WO is used as the target instead of W.

 twenty four

 Even with W / P (ie y value), the capacity maintenance rate is lower than when the target is W. However, even when WZP is greater than 0.5 and less than 0.1, the capacity maintenance ratio is over 60%.

 [0069] The reason for this is not clear, but another study has shown that the reactivity of the organic compound layer 11 and metallic lithium changes depending on the magnitude of WZP (y value). That is, when Li PW O is formed directly on the surface of metallic lithium, and it is left in a dry air environment with a dew point of -40 ° C for 2 weeks, the surface of metallic lithium is observed. Discoloration is seen. When W is used as the target, discoloration is observed when WZP is greater than 0.5, but when Li WO is used as the target, WZP is greater than 1.0.

 twenty four

 Discoloration is seen when That is, it can be seen that even when WZP is greater than 0.5 and less than or equal to 1.0, the reactivity between the inorganic compound layer 11 and metallic lithium is low. Since lithium ions are reduced at the negative electrode 1 during discharge, a similar reaction occurs, and it is assumed that this is the result.

[0070] As described above, the y value which is the molar ratio of the component T to P has an appropriate range. Depending on the target from which the component T is obtained, the appropriate range of X and z values depends on the y value. Each is automatically determined. This is because the valence of each atom is determined as described above. That is, if the target is a transition metal, 2.0 ≤ x ≤ 3.0, 0.01 ≤ y ≤ 0.5, 3.5 ≤ z ≤ 4.0. If the target is a transition metal oxide, then 2.0 ≤x≤3.0, 0.01 ≤y≤l. 0, 3.5≤z≤7.0. In the case of target force lithium oxyacid salt, 2. 0≤x≤7.0, 0. 01≤y≤l. 0, 3.5≤z≤8.0.

[Embodiment 2]

 The conceptual diagram showing the basic structure in the second embodiment of the present invention is the same as FIG. The inorganic compound layer 11 in the negative electrode 1 according to this embodiment is made of a compound having a chemical composition represented by LiMON. M is an element consisting of the element symbols Si, B, Ge, Al, C, Ga and S, and is at least one element selected from the group force. y≤l. 99, 0. 01≤z≤0. 5, or 1. 6≤x≤2. 0, 2. 05≤y≤2. 99, 0. 01≤z≤0. 5, or 1. 6≤x≤2. 0, 3. 05≤y≤3.99, 0. 01≤z≤0. 5, or 4. 6≤x≤5.0, 3. 05≤y≤3.99, 0 01≤z≤0.5. The compound LiMON is also a material with excellent lithium ion conductivity and moisture resistance discovered by the present inventors, and is disclosed in JP-A-2005-38844.

[0072] The bond between component element M and oxygen in LiMON is more thermodynamically stable than the bond between phosphorus and oxygen in lithium nitride phosphate. For this reason, this composition maintains the structure of the solid electrolyte stably even when it comes into contact with water molecules, and suppresses a decrease in ionic conductivity in a humid environment. Further, due to the stability of the inorganic compound layer 11, strong protection of the active material layer 10 that has occluded lithium ions is achieved.

[0073] Thus, in compound LiMON, the bond between component M and oxygen serves to form a more stable bond than the bond between phosphorus and oxygen in lithium nitride phosphate even in a wet environment. . On the other hand, Li MO N is required to exhibit favorable ionic conductivity.

 [0074] From this point of view, when the lithium oxyacid salt is LiBO, LiAlO or LiGaO

 2 2 2

That is, in the above general formula, if component M is B, A or Ga, then 0.6 ≤ x ≤ 1.0, 1. 05 ≤ y ≤ l. 99, and 0.01 01 ≤ z ≤ 0 The power of being 5 ^ Preferred! / ヽ. When the lithium oxalate is Li SiO, Li GeO or Li CO, i.e. in the above general formula

 2 3 2 3 2 3

If the component M force Si ゝ Ge or C, 1. 6≤x≤2.0, 2. 05≤y≤2. 99, And 0. 01≤z≤0.5. When the lithium oxyacid salt is Li SO,

 twenty four

 That is, in the above general formula, when the component M is S, it is preferable that 1.6≤x≤2.0, 3.05≤ y≤3.99, and 0.01≤z≤0.5 . Lithium oxyacid salt is Li AIO

 4. In other words, in the above general formula, if component M is A1, then 4.6 ≤ x ≤

Four

 5. Power of 0, 3. 05≤y≤3.99, and 0.01≤z≤0.5 ^ Preferred! / ヽ.

[0075] X and y can be changed according to the amount and type of lithium oxyacid salt used as a raw material, and z can be changed according to the amount and pressure of nitrogen when forming the inorganic compound layer 11. From the viewpoint of ionic conductivity, the range of z is particularly important. If it is less than 0.01, there will be a problem with ionic conductivity. Conversely, if z> 0.5, the skeletal structure is likely to be destroyed. Impairs ionic conductivity.

[0076] As a method of forming the inorganic compound layer 11 consisting of a compound having a chemical composition represented by Li MO N, a lithium phosphate compound and Li SiO, LiBO, LiA are used as a target.

 2 3 2 lO, Li AIO, Li GeO, LiGaO, Li SO, Li CO, etc.

2 5 4 2 3 2 2 4 2 3

 A method using lithium oxyacid salt is preferred. For the incorporation of N, it is preferable to apply a sputtering method using nitrogen gas or a vapor deposition method in a nitrogen atmosphere to replace some of the oxygen atoms with nitrogen atoms. Instead of the above lithium oxyacid salts, Li O and SiO, GeO, B

 2 2 2

Target oxides of component elements M such as O, Al 2 O, and Ga 2 O or a mixture of these

2 3 2 3 2 3

 Can be used. In such a solid electrolyte, the valences of lithium atom and oxygen atom are +1 and 2 respectively. The nitrogen atom is trivalent. Element M is the same as the valence in the compound used as the target.

[0077] As a method for determining x, y, and z in the prepared LiMON, first, the ratio of the element M is set to 1. Next, calculate the ratio of oxygen atoms and nitrogen atoms to element M by using a method such as nitrogen oxygen analysis (inactive gas impulse heating and melting method). X is calculated using the above valence, assuming that the overall valence is zero.

Other than this, the formation method of the active material layer 10, the form of the current collector 9, the formation method and thickness of the inorganic compound layer 11 are the same as those in Embodiment 1. Further, as in the first embodiment, when the active material layer 10 contains a metal, it is preferable that this metal and at least a part of the current collector 9 form an alloy. [0079] By preparing the negative electrode 1 as described above, the durability of the negative electrode 1 with respect to moisture can be increased, and deterioration of cycle characteristics of a battery using the negative electrode 1 can be suppressed. Such negative electrode 1 can be applied to all lithium batteries that absorb and release lithium ions and use S or Sn as a single element, compound, or alloy as a negative electrode, and its storage characteristics are charge / discharge cycle characteristics. improves.

 When the battery is charged and discharged, lithium is occluded in the active material layer 10 not in direct contact with the electrolyte 3 through the inorganic compound layer 11 and functions as a negative electrode for the first time. That is, the inorganic compound layer 11 faces the electrolyte 3 and serves as a migration path of lithium ions onto the substrate 10 isolated from the electrolyte 3. In this configuration, even if the electrolyte 3 contains moisture, the inorganic compound layer 11 can continue to play the role of an ion transfer path that is not affected by the moisture of the electrolyte 3.

 [0081] The features and effects of Embodiment 2 according to the present invention will be described below with specific examples.

 As an example, an active material layer 10 made of Si is formed on a current collector 9 made of Cu in the same manner as Sample 1 in Embodiment 1, and a compound having a chemical composition represented by LiMON is formed thereon. An inorganic compound layer 11 was formed.

 [0082] For the formation of the inorganic compound layer 11, lithium oxyacid salts shown in (Table 7) were used as targets, respectively, rf magnetron sputtering was used, and sputtering was performed using nitrogen gas. The sputtering conditions were an internal pressure of 2.7 Pa, a gas flow rate of 10 sccm, a high frequency irradiation power of 200 W, and a sputtering time of 20 minutes. The thickness of the obtained inorganic compound layer 11 was approximately 0.15 m. The composition of the inorganic compound layer 11 of each sample is shown in (Table 7).

 [0083] [Table 7] Lithium

 Sample Inorganic compound layer composition Capacity retention rate (%) Oxygenate

2 1 L i 2 S i0 3 L ί ί 0 ^ 0. 69.5

2 2 LiB0 z Lio. 8 BO ,. 45 N 0. 3 63.9

2 3 Li 2 Ge0 3 Li,. 8 GeO 45 N 0. 3 60.6

2 4 L iA10 2 L ί 8 8 10 o. 3 66.0

2 5 Li 6 A10 4 L i 4.A 10 3 .4s 0 3 69.8

2 6 Li 2 C0 3 45 ^ 0. 61.6

2 7 L iGa0 2 Li 0. S GaO ,. 45 N 0. 3 65.8

2 8 Li s S0 4 L i 1.3SO3 s 0 _ 60.9

Comparison sample 1 ― L i 2. sP ^ 3.5 5 0.3 43.4 Using the obtained negative electrode 1 samples 21 to 28, a battery was fabricated in the same manner as in the first embodiment. For comparison, a battery was manufactured in the same manner using Comparative Sample 1 in Embodiment 1. In addition, these batteries were evaluated under the same conditions as in the first embodiment, and as a result, the capacity retention rate after the elapse of 100 charge / discharge cycles is shown in (Table 7).

 [0085] As is clear from (Table 7), the capacity retention rate of Comparative Sample 1 using the inorganic compound layer having LIPON force was 43.4%. On the other hand, the batteries of Samples 21 to 28, in which the inorganic compound layer 11 having a compound power having a chemical composition represented by LiMON was formed, showed a capacity maintenance rate of 60% or more even after 100 cycles. Excellent cycle characteristics were shown.

 Next, an example in which the inorganic compound layer 11 is formed using a mixture of two types of transition metal lithium-containing transition metal oxides as a sputtering target will be described. The lithium oxyacid salt nitride was formed under the same conditions as Samples 21 to 28, except that the lithium oxyacid salt mixture shown in Table 8 (molar ratio 1: 1) was used to form the inorganic compound layer 11. Samples 31 to 43 of the negative electrode 1 on which the inorganic compound layer 11 made of was formed were produced. Except for this, a battery was fabricated under the same conditions as in Embodiment 1, and the cycle characteristics were evaluated. Table 8 shows the composition of the inorganic compound layer 11 and the capacity retention rate after 100 cycles of charge and discharge, which is the evaluation result.

 [0087] [Table 8]

[0088] As is apparent from (Table 8), the batteries of Samples 31 to 43 also showed a capacity retention rate of 60% or more even after 100 cycles, and exhibited excellent cycle characteristics. Like this, nothing In the composition LiMON that forms the organic compound layer 11, the component M may be composed of a plurality of elemental forces. Although data is not shown, the component T in the first embodiment may be composed of a plurality of elements in the same manner.

[0089] Next, the results of studying the range of the z value in the composition formula LiMON are shown. Here, the case where Si is applied as the component M will be described as an example. In preparing samples 21A to 21H shown in (Table 9), an inorganic compound composed of LiSiON with different NZSi, which is the molar ratio of N and Si in the inorganic compound layer 11, by changing the nitrogen pressure in the configuration of sample 21 Layer 11 was formed. NZSi corresponds to Z in the composition formula. The other conditions were in accordance with Sample 21. (Table 9) shows the composition of the inorganic compound layer 11. NZSi was 0.005, 0.01, 0.1, 0.3, 0.5, 0.6, 0.8, 1.0 for samples 21A-21H, respectively.

[0090] [Table 9]

 [0091] Using these samples, a battery was fabricated under the same conditions as in Embodiment 1, and the cycle characteristics were evaluated. Figure 5 shows the capacity retention rate and NZSi after 100 cycles when a battery using a negative electrode composed of Li SiO N with different NZSi formed on the inorganic compound layer 11 was charged and discharged. Shows the relationship. As is clear from Fig. 5, the capacity retention ratio greatly depends on NZ Si, and an improvement effect was observed at 0.01 or higher. Furthermore, the capacity retention rate increased with the increase of NZSi, and a high value from 0.3 to 0.5 was stably obtained. However, when it exceeded 0.5, the capacity retention rate suddenly decreased, and at 0.8, practicality was completely lost. From the above results, NZSi is the most preferred range of force 0.3 or more and 0.5 or less.

[0092] It should be noted that the data shows! /, NA! /, As the component M of Li MO N, B, Ge, Al,

At least one element selected from the group consisting of C, Ga and S, and 0.6 ≤x≤l. 0, 1. 05≤y≤l. 99, 0. 01≤z≤0. 5, or 1. 6≤x≤2. 0, 2. 05≤y ≤2. 99, 0. 01≤z≤0.5, or 1.6≤x≤2.0, 3.05≤y≤3.99, 0.01≤z≤0.5, also ί 4.4.6≤x≤5. 0, 3. 05≤y≤3.99, 0.01≤z≤0.5 【Similar results are obtained here. Although no data is shown, the same result can be obtained when a material other than Si is used for the active material layer 10.

 [0093] It should be noted that the power described in the first and second embodiments taking the coin-type battery as an example, the present invention is not limited to the shape of such a battery.

 Industrial applicability

[0094] The negative electrode for a battery according to the present invention is provided with a negative electrode active material layer that reversibly occludes and releases lithium and contains silicon (Si) or tin (Sn) as a simple substance, a compound, or an alloy, and a negative electrode active material layer thereon. A lithium ion conductive inorganic compound layer. In this negative electrode, the stability of the negative electrode active material layer itself with respect to moisture can be improved, and the cycle characteristics can be greatly improved in a battery using an electrolyte that may be mixed with a minute amount of moisture.

Claims

The scope of the claims
 [1] current collector;
 Provided on the current collector, a compound carrier containing at least one of tin and a single element of tin, a simple substance of silicon, an alloy containing at least one of tin and key, and tin and key. An active material layer containing at least one of the group consisting of:
 A lithium-ion conductive inorganic compound layer provided on the active material layer and having a chemical composition represented by the following general formula (1):
 Battery negative electrode.
 Li PT O (1)
 (However, the component T is at least one element selected from the element group force consisting of the element symbols Ti, Cu, Zr, Mo, Ta, W. ≤y≤l. 0, 3.5 ≤z≤8. 0
[2] General formula (1) [That is, 2. 0≤x≤3.0, 0.01≤y≤0.50, 3.5≤z≤4.0,
 The negative electrode for a battery according to claim 1.
[3] The general formula (1) [here, 2. 0≤x≤3.0, 0. 01≤y≤l. 0, 3.5≤z≤7.0. Claim 1 Negative electrode for batteries.
[4] After charging, the active material layer contains lithium,
 The negative electrode for a battery according to claim 1.
[5] The active material layer contains a metal, and the metal is alloyed with the current collector at a part of the interface with the current collector.
 The negative electrode for a battery according to claim 1.
[6] current collector;
 Provided on the current collector, a compound carrier containing at least one of tin and a single element of tin, a simple substance of silicon, an alloy containing at least one of tin and key, and tin and key. An active material layer containing at least one of the group consisting of:
The lithium is provided on the active material layer and has a chemical composition represented by the following general formula (2). A thium ion conductive inorganic compound layer,
 Battery negative electrode.
 Li MO N (2)
 x y z
 (However, the component M is at least one element in which the element group force consisting of the element symbols Si, B, Ge, Al, C, Ga, S is also selected,
 0. 6≤x≤l. 0, 1. 05≤y≤l. 99, 0. 01≤z≤0. 5,
 1. 6≤x≤2. 0, 2. 05≤y≤2. 99, 0. 01≤z≤0.5,
 1. 6≤x≤2. 0, 3. 05≤y≤3.99, 0.01≤z≤0. 5,
 4. 6≤x≤5. 0, 3. 05≤y≤3. 99, 0. 01≤z≤0.5! ;)
[7] After charging, the active material layer contains lithium,
 The negative electrode for a battery according to claim 6.
[8] The active material layer includes a metal, and the metal is alloyed with the current collector at a part of an interface with the current collector.
 The negative electrode for a battery according to claim 6.
[9] current collector;
 Provided on the current collector, a compound carrier containing at least one of tin and a single element of tin, a simple substance of silicon, an alloy containing at least one of tin and key, and tin and key. An active material layer containing at least one of the group consisting of:
 A lithium ion conductive inorganic compound layer provided on the active material layer and having a chemical composition represented by the following general formula (1):
 An electrolyte that conducts lithium ions;
 A positive electrode that reversibly occludes and releases lithium ions,
 battery.
 Li PT O (1)
 X y z
 (However, the component T is at least one element selected from the element group force consisting of the element symbols Ti, Cu, Zr, Mo, Ta, W, and has the strength 2. 0≤x≤7.0, 0. 01. ≤y≤l. 0, 3.5≤z≤8.0.
[10] current collector; Provided on the current collector, a compound carrier containing at least one of tin and a single element of tin, a simple substance of silicon, an alloy containing at least one of tin and key, and tin and key. An active material layer containing at least one of the group consisting of:
 A lithium ion conductive inorganic compound layer provided on the active material layer and having a chemical composition represented by the following general formula (2):
An electrolyte that conducts lithium ions;
A positive electrode that reversibly occludes and releases lithium ions,
battery.
 Li MO N (2)
 x y z
 (However, the component M is at least one element in which the element group force consisting of the element symbols Si, B, Ge, Al, C, Ga, S is also selected,
 0. 6≤x≤l. 0, 1. 05≤y≤l. 99, 0. 01≤z≤0. 5,
 1. 6≤x≤2. 0, 2. 05≤y≤2. 99, 0. 01≤z≤0.5,
 1. 6≤x≤2. 0, 3. 05≤y≤3.99, 0.01≤z≤0. 5,
 4. 6≤x≤5. 0, 3. 05≤y≤3. 99, 0. 01≤z≤0.5! ;)
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JP4444287B2 (en) 2010-03-31
EP1677375B1 (en) 2015-07-08
EP1677375A4 (en) 2013-03-13
CN1860628A (en) 2006-11-08
US7632607B2 (en) 2009-12-15
JPWO2006043470A1 (en) 2008-05-22
KR100728441B1 (en) 2007-06-13
KR20060085625A (en) 2006-07-27
EP1677375A1 (en) 2006-07-05
US20070020520A1 (en) 2007-01-25
CN100454613C (en) 2009-01-21

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